The present invention relates to 2-acyl-5-substituted thiatetrahydrofuran-4-ones produced by the novel process of our invention and novel compositions using one or more of such 2-acyl-5-substituted thiatetrahydrofuran-4-ones or "cis" or "trans" isomers thereof to alter, modify, augment or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to such consumable materials.
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors to (or in) various consumable materials. These substances are used to diminish the use of natural products, some of which may be in short supply and to provide more uniform properties in the finished product. Coffee-like, roasted, cocoa-like, caramel-like, licorice and roasted almond aroma and flavor characteristics are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors. Sweet, caramel/coffee aromas and flavors prior to smoking and sweet, caramel/coffee, nutty/pyrazine and roasted nutty aroma and taste characteristics on smoking are particularly desirable in tobaccos as well as tobacco flavoring compositions and in tobacco substitutes and flavoring compositions for such tobacco substitutes.
When one mole of diacetyl is reacted with one mole of furfuryl mercaptan, a coffee flavored reaction product is produced which has been found to contain a small percentage (about 10% by weight) of 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone with one mole of the "cis"-"trans" isomers in a ratio to the other of the "cis"-"trans" isomers of about 2:1. The process for preparing such a reaction product (without describing the constituents of the products) is set forth in Swiss Pat. No. 128,720 published on Nov. 16, 1928. It is stated in the Example at Column 2 on page 1 thereof that when one mixes furfuryl-2-mercaptan and diacetyl, the product (alpha-oxy-alpha-acetylethyl)furfuryl-2-sulfide is produced.
U.S. Pat. No. 1,696,419 issued on Dec. 25, 1928 (Title: "Method of Producing Artificial Coffee Aroma") discloses the production of a coffee flavor using:
"One part of diacetyl, four parts of acetyl propionyl, four parts of methyl ethyl acetaldehyde, three parts of acetaldehyde, two parts of alpha methyl furfural, one part of furfural, three parts of pyridine, two parts of isovaleric acid, one part of phenol, one part of isoeugenol, 0.5 parts of guiacol, 0.5 parts of alpha methyl cyclopentenolone, 0.6 parts of methyl mercaptan, 0.3 parts of furfuryl mercaptan, 0.3 parts of n-octyl alcohol and 0.4 parts of thioguiacol" PA1 Hydrogen sulfide; PA1 Formaldehyde; PA1 Formic Acid; PA1 Methanol; PA1 Methyl mercaptan; PA1 Carbon disulfide; PA1 Acetaldehyde; PA1 Acetic acid; PA1 Methyl formate; PA1 Ethanol; PA1 Dimethyl sulfide; PA1 Dimethyl disulfide; PA1 Acrylonitrile; PA1 Acrolein; PA1 Propanal; PA1 Acetone; PA1 Propionic acid; PA1 Acetol; PA1 Methyl acetate; PA1 Ethyl formate; PA1 Methyl ethyl sulfide; PA1 Methyl ethyl disulfide; PA1 Furan; PA1 Thiophene; PA1 Crotonolactone; PA1 Pyrazine; PA1 3-Butene nitrile; PA1 Pyrrole; PA1 Methyl vinyl ketone; PA1 Diacetyl; PA1 Butyrolactone; PA1 Crotonic acid; PA1 i-Butanal; PA1 Butanal; PA1 Butanone; PA1 i-Butyric acid; PA1 Acetoin; PA1 Ethyl acetate; PA1 Furfural; PA1 Pyridine; PA1 2-Pyrrolaldehyde; PA1 2-Methylfuran; PA1 Furfuryl alcohol; PA1 2-Methylpyrazine; PA1 N-methylpyrrole; PA1 Isoprene; PA1 Pentadiene; PA1 Cyclopentanone; PA1 Pentane-2,3-dione; PA1 2-Methyltetrahydrofuran-3-one; PA1 Senecioic acid; PA1 Acetylacetone; PA1 Acetol acetate; PA1 2-Methylbutanal; PA1 3-Methylbutanal; PA1 Valeraldehyde; PA1 2-Hydroxy-3-pentanone; PA1 3-Hydroxy-2-pentanone; PA1 i-Valeric acid; PA1 2-Methylbutyric acid; PA1 Phenol; PA1 5-Methylfurfural; PA1 2-Acetylfuran; PA1 Furfuryl formate; PA1 Dimethylmaleic anhydride; PA1 2-Methyl-3-hydroxy-.gamma.-pyrone; PA1 2-Acetylthiophene; PA1 3-Methylpyridine; PA1 2-Acetylpyrrole; PA1 N-methylpyrrole-2-aldehyde; PA1 5-Methylpyrrole-2-aldehyde; PA1 2,5-Dimethylfuran; PA1 3-Methylcyclopentane-1,2-dione; PA1 2,3-Dimethylpyrazine; PA1 2,5-Dimethylpyrazine; PA1 2,6-Dimethylpyrazine; PA1 Furfuryl methyl sulfide; PA1 2-Methyl-3-ethylacrolein; PA1 1-(2'-furyl)-propane-1,2-dione; PA1 Methyl nicotinate; PA1 Toluene; PA1 m-Cresol; PA1 Guaiacol; PA1 5-Methyl-2-acetylfuran; PA1 Furfuryl acetate; PA1 Methyl ethyl maleic anhydride; PA1 2-Propionylpyrrole; PA1 N-methyl-2-acetylpyrrole; PA1 N-methyl-5-methylpyrrole-2-aldehyde; PA1 2-Propylfuran; PA1 3,4-Dimethylcyclopentane-1,2-dione; PA1 3,5-Dimethylcyclopentane-1,2-dione; PA1 3,3-Diethylcyclopentane-1,2-dione; PA1 3-Methylcyclohexane-1,2-dione; PA1 2,3-Dihydroxyacetophenone; PA1 1-(2'-Furyl)-butane-1,2-dione; PA1 1-[(5'-Methyl)-2'-furyl]-propane-1,2-dione; PA1 2-Butylfuran; PA1 2,2'-Difurylmethane; PA1 N-furfuryl-2-pyrrole; PA1 4-Vinylguaiacol; and PA1 4-Ethylguaiacol. PA1 Acetaldehyde; PA1 Acetic acid; PA1 Acetone; PA1 Acetoxyacetone; PA1 Acrolein; PA1 2-Aminobutane; PA1 n-Amyl acetate; PA1 n-Amyl alcohol; PA1 Amyl butyrate; PA1 Amyl propionate; PA1 2,3-Butaediol; PA1 2,3-Butanedione; PA1 2-Butanon-3-ol; PA1 n-Butyl acetate; PA1 n-Butyraldehyde; PA1 n-Butyric acid; PA1 Caproic acid; PA1 Caprylic acid; PA1 Citronellal; PA1 Crotonaldehyde; PA1 Dimethylamine; PA1 Ethanol; PA1 Ethyl acetate; PA1 Ethylamine; PA1 Ethyl caproate; PA1 Ethyl propionate; PA1 Formic acid; PA1 Geraniol; PA1 3-Heptadecanone; PA1 1-Hexanol; PA1 Hexyl butyrate; PA1 Hexyl propionate; PA1 Isoamyl acetate; PA1 Isoamylamine; PA1 Isobutanol; PA1 Isobutyl acetate; PA1 Isobutylamine; PA1 Isobutyraldehyde; PA1 Isovaleraldehyde; PA1 Linalool; PA1 Linalyl acetate; PA1 Methanol; PA1 Methyl acetate; PA1 Methylamine; PA1 .alpha.-Methylbutyric acid; PA1 Methyl disulfide; PA1 2-Methyl-2-hepten-6-one; PA1 Methyl sulfide; PA1 Methyl trisulfide; PA1 2,4-Octadien-1-ol; PA1 1-Octen-3-ol; PA1 Pelargonic acid; PA1 2,3-Pentadione; PA1 2-Pentyl acetate; PA1 1-Propanol; PA1 2-Propanol; PA1 Propionaldehyde; PA1 Propionic acid; PA1 1-Propyl acetate; PA1 2-Propyl acetate; PA1 Propyl trisulfide; PA1 Triethylamine; PA1 Trimethylamine; PA1 n-Valeric acid; PA1 3-Methyl-1,2-cyclopentanedione PA1 Acetophenone; PA1 Benzaldehyde; PA1 Benzene; PA1 Benzonitrile; PA1 Benzyl alcohol; PA1 Cresol; PA1 3,4-Dihydroxybenzoic acid; PA1 6,7-Dihydroxycoumarin; PA1 Ethyl benzoate; PA1 p-Ethylphenol; PA1 Ethyl phenylacetate; PA1 Eugenol; PA1 Guaiacol; PA1 o-Hydroxyacetophenone; PA1 p-Hydroxybenzoic acid; PA1 p-Hydroxycinnamic acid; PA1 4-Hydroxy-3,5-dimethoxy-benzoic acid; PA1 4-Hydroxy-3-methoxy-benzoic acid; PA1 4-Hydroxy-3-methoxy-cinnamic acid; PA1 o-Hydroxyphenylacetic acid; PA1 p-Hydroxyphenylacetic acid; PA1 p-Methoxybenzoic acid; PA1 4-Methylguaiacol; PA1 Methyl phenylacetate; PA1 Phenol; PA1 Phenyl acetate; PA1 Phenylacetic acid; PA1 Phenylacetic aldehyde; PA1 2-Phenylethyl acetate; PA1 1-Phenylethyl alcohol; PA1 2-Phenylethyl alcohol; PA1 2-Phenylethylamine; PA1 2-Phenyl-2-propanol; PA1 Toluene; PA1 2-Methoxy-4-methylphenol; PA1 .gamma.-Butyrolactone; PA1 .gamma.-Caprolactone; PA1 Furan; PA1 Furfural; PA1 Furfuryl acetate; PA1 Furfuryl alcohol; PA1 2-Furyl methylacetone; PA1 Maltol; PA1 .alpha.-Methyl-.gamma.-butyrolactone; PA1 2-Methylfuran; PA1 Methyl-5-methylfurfuryl sulfide; PA1 2-Methyl-3-tetrahydrofuranone; PA1 .gamma.-Valerolactone; PA1 cis-2-Vinyl-2-methyl-5-(1-hydroxy-1-methylethyl)-tetrahydrofuran; PA1 2-Acetylpyrrole; PA1 2-Formylpyrrole; PA1 1-Methyl-2-formylpyrrole; PA1 5-Methyl-2-formylpyrrole; PA1 Pyrrole; PA1 2,5-Dimethyl-6-ethylpyrazine; PA1 2,6-Dimethyl-3-ethylpyrazine; PA1 2,3-Dimethylpyrazine; PA1 2,5-Dimethylpyrazine; PA1 2,6-Dimethylpyrazine; PA1 2-Ethyl-5-methylpyrazine; PA1 2-Ethyl-6-methylpyrazine; PA1 Methylpyrazine; PA1 Tetramethylpyrazine; PA1 Trimethylpyrazine; PA1 2-Ethyl-3,5,6-trimethylpyrazine; PA1 3-Isoamyl-2,5-dimethylpyrazine; PA1 5-Isoamyl-2,3-dimethylpyrazine; PA1 2-Isoamyl-3,5,6-trimethylpyrazine; PA1 Isopropyl dimethylpyrazine. PA1 Dimethyl naphthalene; PA1 Dodecane; PA1 Methyl diphenyl; PA1 Methyl naphthalene; PA1 Myrcene; PA1 Naphthalene; PA1 Octadecane; PA1 Tetradecane; PA1 Tetramethyl naphthalene; PA1 Tridecane; PA1 Trimethyl naphthalene; PA1 Undecane; PA1 Acetoin; PA1 2-Heptanol; PA1 Linalool; PA1 1-Pentanol; PA1 Isopentanal; PA1 2-Methylbutanal; PA1 2-Heptanone; PA1 2-Methyl-2-hepten-6-one; PA1 2-Octanone; PA1 2-Undecanone; PA1 Benzyl acetate; PA1 Ethyl caprate; PA1 Ethyl caproate; PA1 Ethyl caprylate; PA1 Ethyl cinnamate; PA1 Ethyl laurate; PA1 Ethyl myristate; PA1 Isoamyl acetate; PA1 .gamma.-Nonalactone; PA1 Isovaleric acid; PA1 2-Methylbutyric acid PA1 Lavender essential oil; PA1 Clary sage essential oil; PA1 Rosemary essential oil; PA1 Thyme essential oil; PA1 Fennel essential oil; PA1 Mint essential oil; PA1 Angelica essential oil; PA1 Anise essential oil; PA1 Lemon essential oil; PA1 Wormwood essential oil; and PA1 Cinnamon essential oil. PA1 Diacetyl; PA1 Benzaldehyde; PA1 Furfural; PA1 Furfuryl propionate; PA1 Trimethyl pyrazine; PA1 2,6-Dimethoxyphenol; PA1 Pyruvic acid; PA1 Furfuryl mercaptan; and PA1 Furfuryl acetate. PA1 Beta-ethyl-cinnamaldehyde; PA1 Beta-cyclohomocitral; PA1 Eugenol; PA1 Dipentene; PA1 Damascenone; PA1 Damascone; PA1 Maltol; PA1 Ethyl Maltol; PA1 Delta-undecalactone; PA1 Delta-decalactone; PA1 Benzaldehyde; PA1 Amyl acetate; PA1 Ethyl butyrate; PA1 Ethyl valerate; PA1 Ethyl acetate; PA1 2-Hexenol-1; PA1 2-Methyl-5-isopropyl-1,3-nonadiene-8-one; PA1 2,6-Dimethyl-2,6-undecadiene-10-one; PA1 2-Methyl-5-isopropyl acetophenone; PA1 2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene; PA1 Dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1,b]-furan; PA1 4-Hydroxy hexanoic acid, gamma lactone; and PA1 Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No. 3,589,372 issued on June 29, 1971. PA1 Celery seed oil; PA1 Coffee extract; PA1 Bergamot oil; PA1 Cocoa extract; PA1 Nutmeg oil; and PA1 Origanum oil.
at page 3, column 1, lines 29-39.
No member of the genus of compounds having the structure: ##STR7## (wherein R.sub.1, R.sub.2, R.sub.1 ', R.sub.2 ' and R.sub.3 are defined above) is indicated to be produced as a result of admixing at higher temperatures the foregoing ingredients.
Canadian Pat. No. 1,002,383 issued on Dec. 28, 1976 discloses the preparation of a popcorn-type flavor by reacting glyoxal (an alpha, beta-dicarbonyl compound) with a "sulfide source" at elevated temperatures. The resulting material is indicated to have advantageous properties over reaction products of "sulfide sources" with such materials as 2,3-pentane dione, which is indicated on page 8 to give rise to a product having a "burnt character" when it is reacted with a "sulfide source". Organic "sulfide sources" are also mentioned in Canadian Pat. No. 1,002,383, but are only exemplified by 1-cysteine.
Thus, nothing in the prior art discloses either explicitly or implicitly any member of the genus of the compounds having the structure: ##STR8## wherein R.sub.1, R.sub.2, R.sub.1 ' and R.sub.2 ' are the same or different and each represents hydrogen or methyl and wherein R.sub.3 represents one of C.sub.1 -C.sub.9 alkyl, benzyl, phenyl, substituted or unsubstituted allyl having the structure: ##STR9## substituted or unsubstituted 3-furyl having the structure: ##STR10## (wherein R.sub.4 and R.sub.8 are the same or different and each represents hydrogen or methyl), hydroxyalkyl, oxoalkyl, hydroxycycloalkyl or oxocycloalkyl having the structure: ##STR11## (wherein R.sub.5 and R.sub.6, taken separately, represents hydrogen or C.sub.1 -C.sub.3 alkyl or R.sub.5 and R.sub.6, taken together, complete a cycloalkyl group) and wherein Q is one of the moieties: ##STR12## prepared according to the process of dimerizing one or more alpha, beta-alkane dione(s) to form one or more alpha, beta-alkane dione dimer(s) having the structure: ##STR13## and reacting the said alkane dione dimer(s) in acidic medium and in the presence of a solvent with a mercaptan having the structure: EQU R.sub.3 SH